Fire-resistant finish for textiles comprising zinc fluoroborate

ABSTRACT

FIRE RETARDANT FINISHING COMPOSITIONS, ESPECIALLY USEFUL FOR SYNTHETIC FIBERS, INCORPORATING ZINC FLUOROBORATE AND EMULSIFICATION AND OTHER ADDITIVES TO MAINTAIN THE DESIRABLE HAND AND FEEL OF THE TEXTILE MATERIAL.

United States Patent 01' 3,577,342 Patented May 4, 1971 3,577,342FIRE-RESISTANT FINISH FOR TEXTILES COM- PRISING ZINC FLUOROBORATE LouisIsadore Fidell, Bound Brook, N.J., assignor to American CyanamidCompany, Stamford, Conn.

No Drawing. Continuation-impart of application Ser. No. 647,603, June21, 1967, which is a continuation-in-part of application Ser. No.457,209, May 19, 1965. This application Sept. 2, 1969, Ser. No. 854,750

Int. Cl. C09k 3/28 US. Cl. 252-8.1 4 Claims ABSTRAiIT OF THE DISCLOSUREFire retardant finishing compositions, especially useful for syntheticfibers, incorporating zinc fluoroborate and emulsification and otheradditives to maintain the desirable hand and feel of the textilematerial.

This application is a continuation-in-part of the previously filedapplication Ser. No. 647,603, filed June 21, 1967 and now abandoned,which was a continuation-inpart of previously filed application Ser. No.457,209, filed May 19, 1965, and now abandoned.

This invention relates to a novel fire retardant finishing compositionfor imparting fire retardancy to various textile materials, such ascellulosic materials and synthetic materials, and combinations thereof.More particularly, the fire retardant composition has a high degree ofutility in the treatment of synthetic textile materials which areparticularly highly inflammable in the final commercially availableproducts.

It is frequently desirable to fiameproof synthetic textile fabrics andthe like and other materials made of or containing cellulose acetate andother organic acid esters of cellulose. The flameproofing, to besatisfactory, should impart to the treated materials a high resistanceto burning and/or retard the propagation of a flame when lit, should beinexpensive and easily applied, and should be relatively permanent tolaundering, dry cleaning and the like to which the treated materials arenormally subjected. In addition, the flameproofing should not alter thehand or other physical properties of the treated materials in anobjectionable manner, and should not appreciably affeet the dyeing ofthe said materials.

In recent years, the substantial increase in the use of syntheticmaterials in the form of textile fibers, yarns and fabrics has beenaccompanied by the serious problem of the inflammable nature of thesematerials. Some such materials are not readily inflammable prior totreatment, such as the polyamides or super polyamides which have atendency to ignite, melt, and drip away when fire is applied. However,when these less inflammable materials are treated with binders,stiffening agents, and the like, they become highly inflammable.Polyesters similarly fall into this category. There are other materialswhich do not have especially low temperatures of ignition, but whichwhen once ignited, become highly inflammable. Typical of these materialsare the acrylics. There are in fact, very few synthetic fibers whichwill resist fire and which are not highly inflammable either before orafter treatment with various treating agents conventionally employed.

Prior to this invention, no fully acceptable fire retardant compsoitionswere available. Various prior fire retardant compositions weresuccessful to different degrees in imparting fire retardancy, but theprior fire retardant compositions seriously aflect the normal propertiesof the fibers, yarns or fabrics, properties, such as hand, color, etc.Although there are many substantially satisfactory retardantcompositions for use on cellulose. and cellulose containing textilematerials, such finishes have failed to prove satisfactory for syntheticmaterials for the reasons stated above,

The need for eflicient fire retardant finish which simultaneously,either does not alter hand or improves the hand of the syntheticmaterial being treated is becoming increasingly more important toindustries, such as those involved in clothing, draperies, upholstery,carpets, iugs and the like, in order to provide the public with highquality products and to concurrently remove the substantial hazard ofinflammability.

Typical of an acceptable fire retardant composition for the treatment oftextile substrates, particularly synthetic textile substrates, are: (1)a composition which is easily applied from an aqueous diluent, (2) anon-toxic composition, and (3) a composition which does not adverselyaffect the color or hand of the treated substrate, such as, causingdiscoloration, and/or giving the treated substrate an undesirableharshness.

It is therefore an object of this invention to obtain a compositionwhich imparts a high degree of fire retardancy to an inflammablesubstrate being treated.

Another object is to provide a composition which imparts a high degreeof fire retardancy to synthetic material being treated.

Another object is to provide a composition which, when applied to aninflammable substrate textile material, obtains a high grade of hand.

Another object of this invention is to obtain a process for applying anovel fire retardant composition to an inflammable substrate.

Another object of this invention is to obtain a fire retardant syntheticsubstrate.

Another object is to obtain a process for producing a compositioncapable of imparting fire retardancy and a high grade of hand toinflammable substrates treated with the composition.

Other objects of this invention become apparent from the above andfollowing disclosures.

The objects of this invention are obtained by applying to an inflammablesubstrate a composition which includes (1) zinc fluoroborate, and (2) asecond component selected from the group consisting of (a) a cationicsurfactant-emulsifier together with a cationic organic substance; or (b)a non-ionic surfactant-emulsifier together with a chlorinated paraflin.

A third ingredient necessary to be added, at least prior to theapplication of the above composition to an inflammable substrate, is anaqueous diluent in an amount suflicient to form an aqueous dilution ofthe water-soluble emulsion.

The composition is thereafter applied by any conventional method ofapplication, such as by spraying, dipping, padding and the like.However, incorporation of the material into the fiber dope is alsocontemplated. The treated substrate is subsequently dried atconventional drying temperatures, preferably at a temperature of about250 F. In no event would the drying temperature be above the ignitiontemperature of the fabric.

In the composition of this invention, zinc fluoroborate has no knownequivalent. By the application of zinc fluoroborate solely to aninflammable substrate, fire retardancy may be obtained, but only at thesacrifice of acceptable properties of hand. When the zinc fluoroborateis used alone in aqueous dilutions and applied to textile materials upondrying of the treated textile substrate, the zinc fluoroborate acquiresa crystalline characteristic, thereby leaving the substrate with a harshhand and with a fire retardancy which is less durable than when appliedwith the other components of the composition of this invention.

Therefore, the problem is not solely to obtain fire retardancy. Thetypical problems solved are (1) the obtaining of a fire retardancywithout ruining the commercial acceptability of the hand of thesubstrate being treated, and (2) the obtaining of a durable fireretardant finish.

In the above composition of this invention, a cationic emulsifier isemployed, such as a quaternary amine, for example polyethoxylatedquaternary ammonium salts, and the like, which are formed by reactingfrom about 2 to 20 mols of ethylene oxide with one mol of an adduct of ahigher fatty acid amine and methyl chloride, said fatty acid moietyhaving from about 12 to 20 carbon atoms. This includes fatty acid aminesderived from such fatty acids as stearic, coconut and oleic acids.Whenever a cationic emulsifier is employed, a cationic organic substanceis employed therewith for purposes of the composition of this invention.The cationic organic materials are tertiary amines, such as ethyleneoxide condensation products of primary fatty amines and the like, formedby the reaction of an amine of a higher fatty acid with from 2 to 50mols of ethylene oxide. The higher fatty acid moiety is similar to thatof the cationic organic emulsifier.

In the composition of this invention, the non-ionic surfactantemulsifiers are formed by reaction of from 5 to 25 mols of ethyleneoxide with an adduct of a higher fatty acid and a monocyclic arylcompound. The fatty acid moieties are as described above for thecationic emulsifiers. The non-ionic emulsifiers include for exampleisooctylphenyl polyethoxyethanol, nonylphenol poly-(ethyleneoxy)ethanol, and the like. In the embodiment in which anon-ionic surfactant-emulsifier is employed with the zinc fluoroborate,for the composition of this invention, a chlorinated parafiin is alsoincluded. Any typical chlorinated paraflin having a relatively highdegree of chlorination is suitable. For example, long chain paraffinshaving about 20 to 60, or 50 chlorine substituents are suitable.

Although an acceptable fire retardancy and hand may be obtained by therandom admixing of the essential components of the composition of thisinvention, prior to the application to the treated substrate, in orderto obtain a preferred high degree of fiame retardancy and concurrentlyobtain a high quality hand characteristically desired for textilesubstrates, it is advantageous that a specific method be employed toobtain the fire-retardant composition of this invention.

In the embodiment which employs the non-ionic surfactant-emulsifier andchlorinated parafiin, the emulsion is prepared by first blending theemulsifier with the wax (chlorinated parafiin) and thereafter addingthereto a sufiicient amount of water to form a thin paste. Preferablywhile agitating the thin paste, zinc fluoroborate in a diluted form isadmixed with the thin paste, followed 4 by adding the remainder of theaqueous diluent with the agitation preferably continuing until a fine,stable emulsion is obtained.

In the embodiment employing a cationic emulsifier and a cationic organicsubstance, the cationic emulsifier and the cationic organic substanceare each separately blended with an aqueous diluent, and thereafter theaqueous cationic organic substance is added to the aqueous cationicemulsifier, and substantially thereafter the zinc fluoroborate is addedto the mixture of the cationic organic substance and cationicemulsifier. During each addition, agitation preferably is employed.

In preparing the composition of this invention, zinc fiuoroborate isnormally employed in an amount ranging from about 10% to about 30%, andpreferably from about 5% to about 20% based on the weight of the finalcomposition following the addition of water. The chlorinated parafiin isnormally employed in a range of from about 0.25% to about 2.0%,preferably at about 0.5% to about 1.5%. The non-ionic emulsifier isnormally employed in a range from about 0.1% to about 1.5%, preferably0.5% to about 1.0%. The cationic emulsifier is normally employed in arange of from about 1% to about 1.5%. The cationic organic substance isemployed in a range of about 0.5% to about 3%, preferably from about 1%to about 1.5%.

The amount of aqueous diluent added will depend upon the substrate beingtreated and the amount of wet pickup of the substrate to be employed.

The following examples are for purposes of illustrating the inventionand are not intended to limit the scope thereof, except as limited inthe appended claims.

In the following examples the following test method was employed todetermine the fire retardancy of the treated substrates.

Methenamine pill test for fire-retardancy of textile material Amethenamine pill Weighing 0.33 gram- (5 grains) is placed on the surfaceof the carpet or fabric. Using a match, the pill is ignited and remainsso until completely consumed (2 /2 minutes).

The flammability or combustion of the surface fibers is observed andrecorded as is the effect of the burning pill on the backup fabric ofthe substrate being tested.

EXAMPLE I A wax-fluoroborate emulsion was prepared using the followingformula.

Ingredients: Parts by wt. Zinc fluoroborate (40% soln) 50.0 Chlorinatedparaflin 1 1.0 Emusifier (non-ionic) 0.5 Water 48.5

Total 100.0

1 Chlorofin 5 0, Hercules Powder, Inc. 2 Condensatwn product of 1 mole nonyl phenol plus 9.5 moles ethylene oxide. (Decerosol 50 AmericanCyanamid Co.)

The above emulsion is prepared by blending the emulsifier with the waxand adding thereto enough water to form a thin paste. To this is addedslowly (with agitation) diluted zinc fluoroborate. The remainder of thewater required is further added and agitation continued until a finestable emulsion is the resultant product.

EXAMPLE II Aqueous dilutions of the product of Example I are applied toin pile tufted acrylic carpeting containing a cotton back by spraying,whereupon amounts of either 7.5, 5.5, or 3.5 percent total solids wereapplied. The treated carpets were dried at 250 F.

Methenamine pill tests for combustion and flammability were made inaccordance to the aforementioned test procedure. Results are shown inTable I.

6 EXAMPLES VII-IX Additional formulations were made according to ExampleV substituting as follows:

Cationic organic substance Cationic emulsifier Example:

VII Ethomeen 18/12 1 Ethoquad (342. VIII..- Ethomeen C-20 l Ethoquad0-12. IX .1 Ethomeen C- 1 Ethoquad C-12.

1 Tertiary amines: ethylene oxide condensation products of primary fattyamine (Armour Co.).

2 Polyethoxylated quaternary ammonium salts (Armour 00.).

Results show good resistance to fire as obtained on both the pileacrylic fiber and the cotton backing of the treated rug sample.

EXAMPLES III AND IV Additional formulations were made according to Ex-25 ample I, substituting as follows:

The compositions of Examples VII, VIII and IX gave similar fireretardant properties to that of Example V.

It is within the scope of this invention to make such modifications ofthe compositions and processes disclosed herein as would be obvious to aperson of ordinary skill in this art, and it is to be understood thatthe examples illustrating this invention are intended to limit the scopeExample Chlorinated parafiin Non-ionic emulsifier III Clorofin 28(Hercules Powder Co.)- Istliptylphenyl polyethoxy ethanol (Triton X-100,Rohm dz aas IV Clorofin 40 (Hercules Powder C0.) Nonylphenolpoly(ethyleneoxy)ethano1 (Igepal 00-710,

Antara Chemical 00.).

Note: In Examples I to IV the numbers on the chlorinated paraffinsrepresent numbers of chlorine substituents on long chain alkanes orparaflin hydrocarbons.

The compositions of Examples III and IV gave similar fire-retardantproperties to that of Example I.

EXAMPLE V An emulsion was prepared in the following manner: Ingredients:Parts by Wt. Zinc fluoroborates 5.0 Water 15.0

The zinc fluoroborate is dissolved in the water with stirring.

1A tertiary amine which is an ethylene oxide condensation product ofstearyl amine and 50 moles ethylene oxide (Armour 2 Retarder 895, aquaternary amine (Proctor Chemical 00.).

Products (B) and (C) are each blended with Water and then (B) added to(C). Product (A) is then added to this mixture with stirring.

EXAMPLE VI 15 milliliters of the formula of Example III is sprayed onto30 inch square portions of acrylic or acrylic face cotton back pilefabric. After air drying and conditioning the treated pile fabrics aretested by the Methenamine Pill Test Method. Results shown in Table II.

TABLE II Fabric: Methenamine pill test Acrylic-treated Melted, did notburn. Untreated Fuses and supports flame. Acrylic/cotton-treated Melted,did not burn. Untreated Fuses and supports flame.

only insofar as is stated in the specification and as the followingclaims are limited.

I claim:

1. A fire-retardant composition consisting essentially of zincfiuorobor-ate and a material selected from the group consisting of (a)from about 0.5 to 3% of a cationic emulsifier formed by reacting from 2to 20 moles of ethylene oxide with one mol of an adduct of a higherfatty acid amine and methyl chloride and from about 0.5% to about 3% ofa cationic polyethylene oxide tertiary amine formed by the reaction ofthe amine of a higher fatty acid with from 2 to mols of ethylene oxide;and (b) from about 0.1 to 1.5% of a non-ionic surfactant emulsifier,formed from 5 to 25 mols of ethylene oxide and an adduct of a higherfatty acid and a monocyclic aryl compound, and from about 0.25 to 2% ofa chlorinated paraflin having from 20 to chlorine groups; and water,said zinc fluoroborate being present in the amount ranging from about 5%to about 30%, said percentages being based on total weight of thecomposition after addition of said water.

2. A fire-retardant textile material including the fireretardantcomposition of claim 1 in an amount sufficient to impart fireretardancy.

3. The textile material of claim 2 wherein said textile is synthetic.

4. The textile material of claim 3 wherein said textile material is anacrylic fiber.

References Cited UNITED STATES PATENTS 2,695,243 11/1954 Kosmin117-139.5 2,948,641 8/1960 McCluer 2528.1 3,038,820 6/1962 Albrecht1l7-139.5 3,082,121 3/1963 Donaldson et al 2528.1

JOHN T. GOOLKASIAN, Primary Examiner D. I. FRITSCH, Assistant ExaminerUJS. Cl. X.R.

